EP0383002B1 - Tuile en béton revêtue - Google Patents

Tuile en béton revêtue Download PDF

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Publication number
EP0383002B1
EP0383002B1 EP90100106A EP90100106A EP0383002B1 EP 0383002 B1 EP0383002 B1 EP 0383002B1 EP 90100106 A EP90100106 A EP 90100106A EP 90100106 A EP90100106 A EP 90100106A EP 0383002 B1 EP0383002 B1 EP 0383002B1
Authority
EP
European Patent Office
Prior art keywords
weight
copolymer
roof tile
units
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90100106A
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German (de)
English (en)
Other versions
EP0383002A1 (fr
Inventor
Bernhard Dr. Dotzauer
Rolf Dr. Dersch
Johannes Dr. Vinke
Harutyun Dr. Hanciogullari
Manfred Dr. Schwartz
Volkmar Dr. Berg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0383002A1 publication Critical patent/EP0383002A1/fr
Application granted granted Critical
Publication of EP0383002B1 publication Critical patent/EP0383002B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/4857—Other macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/63—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D1/00—Roof covering by making use of tiles, slates, shingles, or other small roofing elements
    • E04D1/28—Roofing elements comprising two or more layers, e.g. for insulation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • the present invention relates to a coated concrete roof tile with improved properties and a method for its production.
  • Concrete roof tiles are made from mortars, the consistency of which enables the final shape.
  • the shape of the roof tiles is retained even during the hardening process, which usually takes place at temperatures between 40 and 100 ° C.
  • Concrete roof tiles tend to efflorescence; these arise from the reaction of calcium hydroxide on the surface of the roof tiles with the carbon dioxide from the air. Calcium hydroxide can get onto the surface of the roof tiles during curing, but also in the weather. The result is blotchy, unsightly roofs.
  • the mostly solid-colored concrete roof tiles are covered with coating compounds on the surface after shaping, but before hardening, i.e.
  • green stones which are intended to prevent lime efflorescence on the surface of the roof covering materials, and are then stored in hardening chambers for 6 to 12 hours which usually prevail at the above temperatures, stored; during this time they harden and at the same time the coating mass dries. Sometimes a further application with coating compound is carried out after curing with subsequent drying.
  • MFT film-forming temperature
  • PVC pigment volume concentration
  • emulsion polymers based on n-butyl acrylate or 2-ethylhexyl acrylate and styrene have been used as binders, the MFT of the polymer dispersions on which they are based always being around 20 ° C and that of the coating systems around 5-8 ° C.
  • roofs whose concrete roof tiles were manufactured in autumn or winter and laid out shortly afterwards are at risk.
  • Another task was to find a concrete roof tile equipped with algicide without polluting the environment with toxic substances. Finally, the task was to find a method for producing such a concrete block that does not use any additives or auxiliary substances that can pollute the wastewater or groundwater when disposing of waste.
  • aqueous dispersion of copolymer A which has a viscosity at 23 ° C. of 0.5 to 2.5 Pa.s and preferably a pH of about 8.
  • the organotin compounds of the type mentioned under A1 are known or can be obtained by known processes.
  • Such connections may be mentioned: tri-n-butyltin acrylate, tri-n-butyltin methacrylate, tri-cyclohexyltin methacrylate, tri-cyclohexyltin acrylate, tri-phenyltin acrylate, triphenyltin methacrylate, tri-n-propyltin acrylate, tri -n-propyltin methacrylate, tri-isopropyltin acrylate, tri-isopropyltin methacrylate, tri-sec.-butyltin acrylate, tri-sec.-butyltin methacrylate, tri-ethyltin acrylate, tri-ethyltin methacrylate, diethyl -butyltin acrylate, diethylbutyltin methacrylate, diethylamylt
  • organotin compounds which contain an acrylic or methacrylic group and three alkyl groups with 3 to 6 carbon atoms bonded to the tin are particularly effective. Of these, tri-n-butyltin methacrylate is preferred because of its easy accessibility.
  • the monomers mentioned under A2 can, provided they carry carboxyl or sulfonic acid groups, be present in the copolymers A in the form of the free acids or in completely or partially neutralized form, in particular in alkali metal or ammonium salt form.
  • Monomers A3 containing carbonyl groups are monomers with at least one aldo- or keto group and a polymerizable double bond.
  • Of particular interest are acrolein, diacetone acrylamide, formylstyrene, vinyl alkyl ketones preferably having 4 to 7 carbon atoms, such as especially vinyl methyl ketone, vinyl ethyl ketone and vinyl isobutyl ketone and / or (meth) acryloxy-alkylpropanals of the general formula in which R1 represents -H or CH3, R2 represents -H or an alkyl radical containing 1 to 3 carbon atoms, R3 represents an alkyl radical containing 1 to 3 carbon atoms and R4 represents an alkyl radical containing 1 to 4 carbon atoms.
  • Such (meth) acryloxyalkylpropanals can be prepared by the process of German patent application P 27 22 097.9 by esterification of ⁇ -hydroxyalkylpropanals of the general formula in which R2, R3 and R4 have the meaning given above, in the presence of inert diluents and small amounts of sulfonic acids and mineral acids at temperatures from 40 to 120, in particular from 60 to 90 °.
  • Suitable monomers bearing keto groups are also diacetone acrylate, acetony acrylate, diacetone (meth) acrylate, 2-hydroxypropyl acrylate acetylacetate, butanediol-1,4-acrylate acetylacetate and 2-ketobutyl (meth) acrylate.
  • the amount of the copolymerized comonomers containing carbonyl or keto groups is preferably 1 to 4% by weight, based on the copolymers A.
  • the monomers of the group mentioned under A4 provide by far the largest proportion of the copolymer A. Therefore their nature and their proportions are largely responsible for the glass transition temperature of a copolymer A.
  • the legalities to be observed here are known to the person skilled in the art. They are therefore only briefly outlined here: a distinction is made between hardening and softening monomers.
  • hardening or softening refer to those monomers which are sometimes given inaccurately in the literature as “hard” or “soft”, ie those monomers which, when polymerized, give hard or softer homopolymers.
  • hardening monomers are generally understood to be those whose homopolymers have glass transition temperatures of about 25 to 120 ° C., and plasticizing monomers those whose homopolymers have glass transition temperatures of about -60 to + 25 ° C. As is known, there are smooth transitions between these monomer groups, but typical representatives of both are known.
  • Typical hardening monomers are e.g. Styrene, methyl methacrylate and tert-butyl acrylate. Of these, methyl methacrylate and styrene are preferred in the context of the present invention.
  • Typical plasticizing monomers are e.g. Acrylic and methacrylic acid esters of 2 to 8 carbon atoms containing non-tertiary alkanols. Of these, n-butyl acrylate, n-butyl methacrylate and ethylhexyl acrylate are preferred in the context of the present invention.
  • the glass transition temperatures of the copolymers A are also influenced by the additional incorporation of the monomers mentioned under A1 to A3. Therefore, an adjustment of the quantitative ratios of the monomers A4 given above may have to be made.
  • the glass transition temperature can be determined using customary methods, e.g. from measuring the modulus of elasticity in a creep test as a function of temperature or using differential thermal analysis (DTA) (see A. Zosel, Aid und Lack 82 (1976), 125-134) .
  • DTA differential thermal analysis
  • the aqueous dispersions of the copolymer A can be prepared in a conventional manner by copolymerizing the monomers A1 to A4 in an aqueous emulsion using the customary emulsifying and dispersing auxiliaries and usually have a copolymer A concentration of 40 to 60% by weight.
  • emulsifiers and dispersants they usually contain 0.2 to 3% by weight, based on the amount of copolymer A, anionic and / or nonionic emulsifiers, such as sodium dialkylsulfosuccinates, sodium salts of sulfated oils, sodium salts of alkylsulfonic acids, sodium and potassium and ammonium alkyl sulfates, alkali metal salts of sulfonic acids, oxalkylated C12 to C24 fatty alcohols and oxalkylated alkylphenols, and also oxyethylated fatty acids, fatty alcohols and / or fatty amides, oxyethylated alkylphenols, and also sodium salts of fatty acids, such as sodium stearate and sodium oleate.
  • anionic and / or nonionic emulsifiers such as sodium dialkylsulfosuccinates, sodium salts of sulfated oils
  • Emulsifiers, fatty alcohol sulfates and fatty alcohol ethoxylates are preferably used, since these are particularly readily biodegradable. This gives finely divided dispersions which are outstandingly suitable for the invention.
  • the average particle size of the dispersions according to the invention is usually well below 100 nm.
  • Component (B) namely at least one water-soluble dihydrazide of an aliphatic dicarboxylic acid containing 2 to 10, preferably 4 to 6 carbon atoms, is added to the dispersions of the copolymers A, advantageously in an amount of 0.05 to 1, preferably 0 , 4 to 0.6 mol per mol of the carbonyl groups contained in the copolymers A.
  • components (B) include: oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide and / or itaconic acid dihydrazide.
  • the dispersions of copolymers A containing the components (B) form glossy, clear and tough-flexible films at room temperature, which absorb only a little water. After 24 hours' storage in water, less than 10, mostly less than 5% are measured. They are free from plasticizers and film-forming agents.
  • the dispersions have little tendency to foam, but it may be advantageous to use defoamers for processing into coating compositions.
  • Suitable defoamers are, for example, silicone-based products.
  • organo-tin compounds mentioned above are completely incorporated into the polymer chains, and they are also very stable to hydrolysis. So you can measure in the serum of the copolymer A dispersions tin concentrations of about 1 ppm, regardless of whether 0.1 or 5% organo-tin compound was used.
  • Dispersions of copolymers A are therefore to be classified more favorably than those which contain zinc dithiocarbamate and / or benzimidazole derivatives which are sparingly soluble as biocid finishing according to the prior art.
  • the LC50 gold orfe is below 500 mg / l.
  • the very low concentration of the tin which is very resistant to hydrolysis, prevents growth by algae such as Chlorella vulgaris.
  • inorganic fillers and color pigments are incorporated into the dispersions of the copolymers A containing the components (B) and the desired viscosity is adjusted with water.
  • examples of inorganic fillers are considered: chalk, quartz powder and / or heavy spar.
  • color pigments are iron oxide red or black pigments.
  • the pigment volume concentration of this formulation is about 45%, the viscosity is 150 mPa.s (82 S ⁇ 1), measured according to DIN 53 018.
  • the concrete roof tile is made in the usual way from ready mixed concrete by an extrusion process. It already gets its final shape.
  • the coating composition is applied in a manner known per se, preferably by spraying, to the "green roof tile", ie to the still wet concrete. The total application is approx. 300 g / m2 (dry).
  • the coated roof tile is coated in a so-called chamber is introduced, where the concrete is set in a 6 to 12-hour setting process at temperatures of 40 to 65 ° C. and the copolymer of the coating composition is filmed.
  • the roof tile is preferably sprayed with the coating compound a second time. Drying takes place in a tunnel oven at ambient air temperatures around 100 ° C. The tunnel kiln and the subsequent cooling section are designed so that a complete filming takes place.
  • the very even coatings have a very good barrier effect against calcium ions. They show no lime efflorescence after the water bath treatment.
  • the longevity of the coatings which is determined in the freeze-thaw alternation test, is a particularly surprising feature of a method for rapid weathering customary in the concrete roof tile industry based on DIN 52 104.
  • the roof tiles according to the invention survive at least twice as much, namely at least 1200, freeze-thaw Change without damage such as that of the prior art, in which damage can be expected after 300 to 600 freeze-thaw changes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Civil Engineering (AREA)
  • Architecture (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Press-Shaping Or Shaping Using Conveyers (AREA)
  • Devices For Post-Treatments, Processing, Supply, Discharge, And Other Processes (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • On-Site Construction Work That Accompanies The Preparation And Application Of Concrete (AREA)
  • Manufacturing Of Tubular Articles Or Embedded Moulded Articles (AREA)
  • Glass Compositions (AREA)

Claims (4)

  1. Tuile de couverture en béton dont au moins l'une des surfaces est revêtue d'un film d'un copolymère, chargé éventuellement d'additifs et/ou de pigments, caractérisée en ce que le copolymère contient les unités monomériques suivantes, incorporées par polymérisation :
    (a) 0,03 à 2% en poids d'étain, sous forme d'unités d'au moins un composé d'organoétain avec une ou plusieurs liaisons C=C,
    (b) 0,5 à 5% en poids d'unités acide acrylique, acide méthacrylique, acrylamide, méthacrylamide et/ou acide vinylsulfonique,
    (c) 0,1 à 5% en poids d'unités de monomères présentant des radicaux carbonyle, qui sont réticulées avec des dihydrazides d'acides dicarboxyliques aliphatiques contenant 2 à 10 atomes de carbone et
    (d) la différence jusqu'à 100% en poids, d'unités d'au moins deux monomères appartenant au groupe des esters des acides acrylique et méthacrylique d'alcanols en C₁ à C₈ et du styrène, avec un choix tel et en proportions quantitatives telles que le copolymère possède, avant la réticulation, une température de transition vitreuse de -15 à +10°C.
  2. Tuile de couverture en béton suivant la revendication 1, caractérisée en ce qu'elle est revêtue d'un copolymère qui contient, à titre d'unités d'un composé d'organoétain, des unités méthacrylate de tri-n-butylétain.
  3. Procédé de fabrication d'une tuile de couverture en béton suivant la revendication 1, caractérisé en ce que l'on applique sur au moins une surface de la tuile de couverture à l'état "vert", une préparation aqueuse qui contient
    (A) un copolymère dispersé de
    (A₁) 0,03 à 2% en poids (calculés sous forme d'étain) d'au moins un composé d'organoétain avec une ou plusieurs liaisons C=C polymérisables,
    (A₂) 0,5 à 5% en poids d'acide acrylique, d'acide méthacrylique, d'acrylamide, de méthacrylamide et/ou d'acide vinylsulfonique,
    (A₃) 0,1 à 5% en poids d'au moins un ou plusieurs monomères présentant des radicaux carbonyle et
    (A₄) la différence jusqu'à 100% en poids d'au moins deux monomères appartenant au groupe des esters de l'acide acrylique et de l'acide méthacrylique d'alcanols en C₁ à C₈ et du styrène en un choix tel et en proportions quantitatives telles que le copolymère possède une température de transition vitreuse de -15 à +10°C,
    (B) 0,2 à 5% en poids (par rapport au copolymère sec) d'au moins un dihydrazide soluble dans l'eau d'un acide dicarboxylique aliphatique contenant de 2 à 10 atomes de carbone,
    (C) 1 à 5% en poids (par rapport au copolymère sec) d'au moins un émulsif appartenant au groupe des sulfates d'alcools gras et des éthoxylates d'alcools gras
    et
    (D) jusqu'à 300% en poids (par rapport au copolymère sec) de pigments colorants et/ou d'additifs ou de granulats minéraux,
    on laisse ensuite sécher la préparation, au cours du durcissement à chaud de la tuile de couverture en béton, en un film et on applique éventuellement après le durcissement à chaud, une couche supplémentaire de la préparation que l'on laisse également sécher en un film.
  4. Procédé suivant la revendication 3, caractérisé en ce que l'on applique la préparation en une proportion telle sur la tuile de couverture que la proportion appliquée totale (à sec) varie de 50 à 300 g/m².
EP90100106A 1989-01-16 1990-01-04 Tuile en béton revêtue Expired - Lifetime EP0383002B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3901073A DE3901073A1 (de) 1989-01-16 1989-01-16 Betondachstein
DE3901073 1989-01-16

Publications (2)

Publication Number Publication Date
EP0383002A1 EP0383002A1 (fr) 1990-08-22
EP0383002B1 true EP0383002B1 (fr) 1994-06-22

Family

ID=6372157

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90100106A Expired - Lifetime EP0383002B1 (fr) 1989-01-16 1990-01-04 Tuile en béton revêtue

Country Status (9)

Country Link
US (1) US5047295A (fr)
EP (1) EP0383002B1 (fr)
JP (1) JPH02233572A (fr)
AT (1) ATE107616T1 (fr)
AU (1) AU619071B2 (fr)
DE (2) DE3901073A1 (fr)
DK (1) DK0383002T3 (fr)
FI (1) FI95126C (fr)
NO (1) NO179000C (fr)

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ES2726045T3 (es) 2010-12-21 2019-10-01 Basf Se Dispersiones de polímero en varias etapas, procedimiento para su fabricación y su uso
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BR112014030294A2 (pt) 2012-06-05 2017-06-27 Basf Se uso de uma dispersão de polímero aquosa de múltiplos estágios, folha metálica, e, método para revestir folhas metálicas
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DE2854107C3 (de) * 1978-12-14 1981-11-12 Kubota Ltd., Osaka Dachdeckplatte
JPS58118868A (ja) * 1982-01-07 1983-07-15 Nippon Paint Co Ltd 防汚塗料用樹脂組成物
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US4670481A (en) * 1986-02-14 1987-06-02 Ameron, Inc. Organotin acrylate and organotin polysiloxane antifouling coating composition

Also Published As

Publication number Publication date
US5047295A (en) 1991-09-10
AU4796690A (en) 1990-07-19
FI900211A0 (fi) 1990-01-15
NO900191D0 (no) 1990-01-15
AU619071B2 (en) 1992-01-16
EP0383002A1 (fr) 1990-08-22
DE3901073A1 (de) 1990-07-19
DK0383002T3 (da) 1994-07-25
NO179000B (no) 1996-04-09
FI95126C (fi) 1995-12-27
ATE107616T1 (de) 1994-07-15
FI95126B (fi) 1995-09-15
JPH02233572A (ja) 1990-09-17
DE59006163D1 (de) 1994-07-28
NO179000C (no) 1996-07-17
NO900191L (no) 1990-07-17

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